An Unexpected Pathway in the Cage Opening and Aggregation of P₄

Abstract

Gefühlvoller Abbau: Die Reaktion des [(Me3Si)3Si]−‐Anions mit weißem Phosphor ergibt ein neues Dianion, das augenscheinlich aus der unerwarteten Zusammenlagerung von zwei [RP4]−‐Einheiten zu einem nortricyclischen P7‐Gerüst mit einem anionischen exo‐P‐Atom resultiert (siehe Schema; R=Si(SiMe3)3). Diese Reaktion beleuchtet den Mechanismus des P4‐Abbaus durch Nucleophile und den Einfluss von Silylsubstituenten auf die Produktbildung.

Controlling the Activation of White Phosphorus: Formation of Phosphorous Acid and Ruthenium‐Coordinated 1‐Hydroxytriphosphane by Hydrolysis of Doubly Metalated P4

“…Research in this field has led to the synthesis of an amazing variety of transition-metal complexes containing P n units originating from either the coupling or the degradation of the cage molecule(s) as well as from the recombination of smaller fragments into polyatomic aggregates. [1] These compounds often contain species with unique geometric and electronic properties which, apart from exhibiting a rich and intriguing chemistry, [1][2][3] have found interest either as building blocks for the construction of networks of mono-and polydimensional inorganic structures [4] or as phosphorustransfer agents towards inorganic and organic molecules. [5] The recent activation of white phosphorus with either heterocyclic carbenes [6] or highly nucleophilic main group compounds [1][2][3]7] has led to new opportunities in this area, especially by allowing the partial degradation of the molecule and its functionalization by insertion of organic fragments into the assembled polyphosphorus units without the involvement of a transition metal.…”

“…[1] These compounds often contain species with unique geometric and electronic properties which, apart from exhibiting a rich and intriguing chemistry, [1][2][3] have found interest either as building blocks for the construction of networks of mono-and polydimensional inorganic structures [4] or as phosphorustransfer agents towards inorganic and organic molecules. [5] The recent activation of white phosphorus with either heterocyclic carbenes [6] or highly nucleophilic main group compounds [1][2][3]7] has led to new opportunities in this area, especially by allowing the partial degradation of the molecule and its functionalization by insertion of organic fragments into the assembled polyphosphorus units without the involvement of a transition metal. [2a, 3e, 5] Previous work from our group has highlighted the utility of {Cp R RuL 2 } moieties (Cp R = C 5 H 5 , C 5 Me 5 ; L = phosphane) for coordinating the intact P 4 molecule in reactions that yield stable mono- [8] or dinuclear [9] cationic complexes [{Cp R RuL 2 } n (h 1 -P 4 )] n+ (n = 1, 2).…”

Carbene Activation of P4 and Subsequent Derivatization

“…This aim has not yet been reached, but coordination and functionalization of P 4 by transition-metal complexes, leading to a variety of P x nÀ ligands, have been investigated extensively. [3,4] Noteworthy is the elegant work of the Cummins group using P 4 to produce P 1 and P 2 niobium complexes that can be used as phosphorustransfer agents.…”

One‐Pot Syntheses of Cationic Polyphosphorus Frameworks with Two‐, Three‐, and Four‐Coordinate Phosphorus Atoms by One‐Pot Multiple PP Bond Formations from a P1 Source

“…A related tetraphosphete ( 3 ) has been previously prepared 4. The formation of 6 a + is then initiated by a nucleophilic attack of 17 on the three‐coordinate phosphorus atom of 5 + according to Scheme 23. This attack most likely results in the cleavage of the PP bond involving one of the four‐coordinate P atoms and the formation of intermediate 18 + .…”